Dicyandiamide phenolaldehyde resin varnish and process of preparation



1958 J. F. BOINEY I ,824,849

DICYANDIAMIDE PHENOLALDEHYDE RESIN VARNISH AND PROCESS OF PREPARATION Filed April 26, 1956 Time in Minutes WITNESSES INVENTOR Joesph F Boiney United States Patent 9 DICYANDIAMIDE PHENOLALDEHYDE RESIN VARNISH'AND'PROCESS OF PREPARATION Joseph F. Boiney, Hampton, S. C., assignor to Westinghouse Electric Corporation, East'Pittsbnrgh, Pa., a corporation of Pennsylvania ApplicatiouApril'26, 1956; Serial'No. 580,862

4 Claims. (Cl. 260--33.4)

This inventionrelatestothe preparationof novelr-esinous varnish compositionsto. be employed. inpreparing relatively. thick.fire-resistant thermoset laminatestherefrom and the products-so produced- It has been.desirable to 'haveavailable, particularly in the electrical industry, resinouslaminatescthat are highly fire-resistant while possessing good electrical resistance properties, both dry and when subjected to humidification, as wellas .havinghigh strength and other physicalproperties. Resinous. laminates. of. this: type in the forms of plates, tubes, channels, anglesand other formsareparticularly. desirable for use in switchgear, switchboards, tap changersandisimilar. electrical apparatus that may be subjected. to electrical. arcs. due. to: opening of. electrical: contacts.

Highly: fire-resistant laminates with excellent mechanical and electrical. properties. have.v been: prepared: by" employing. the. phenol?dicyandiamide-formaldehyderesin varnish. composition. disclosed in the. application of David E. Baldwin et.al., SerialsNumber; 443,720, filed July 1954,.now PatentzNo..2,80l 672, and'assigned to the same assignee as.thepresentinventions However; a'strong-exothermic reaction takesplacezduring the molding of. lami nates comprising. a. phenol-dicyandiamiderformaldehyde resiilandzsheet fibrous: material. This exothermiereaction becomes progressively more difficult' to controlas; the thickness of the laminate increases. is incurred during the molding oflaminates up to /2 inch in thickness because the heat evolved is dissipated to'the platen' plates rapidly'enough' so that the'laminate does not char, crack or decompose.

In the manufacture of laminates of a thickness. of. gre'ater'than /2 inch, it is difiicult' to control the rate of outputofheat'resulting from the exothermic reaction and as a result the laminate has large burned areas near the center,.rendering the laminate useless. Such thick. laminateshavealso exploded in the press, causing pieces. of. thelaminateto fly in all directions.

It is .desirable in many applications'to employ laminated members havinga thickness of from /2 inch to 2 inches or more in thickness. In addition to the excellent fireresistant. properties possessed by phenol-dicyandiamideformaldehyde laminates, properly molded laminates possess outstanding mechanical and electrical properties and may be employed for many applications where fire resistance isnot particularly important.

The object of the invention is to provide for producingthermosettable resinous reaction productsv by reacting phenol, dicyandiamide and formaldehyde to provide.

A-stage resin of such nature that it possesses low exo-- thermic reaction when applied to fibrous sheet. material. and'cured under heat and pressure.

A further object of the invention is to provide rela@ tively thick thermoset laminates comprising afibrous'sheet material. and a thermoset reaction product of phenol, di-- cyandiamide and formaldehyde, which thick laminates No great difiiculty 2,824,849 Patented Feb 25, 1958.

havea highfire resistance, good electricalinsulating properties and high physical strength.

Other objects of. the invention will, in part, be obvious and will, in part, appear hereinafter.

For a better understanding of the nature and objects ofv the invention, reference should be had to the following. detailed description and drawing in which the single. figure is a graph plotting time against temperature. for a molding cycle.

I have found a novel. process for preparingphenohdi cyandiamide-formaldehyde. resins sov that the. exothermic reaction that takes. place during. molding; of the. resinous laminatesrwiil be reduced considerably and'will result in the ability to manufacture laminates of greater thickness thanv heretofore possible. Thisisl attained by mixing-and reacting the various resin components-together in a certain specified order. andunder certain particular conditions..

The resin varnish-of this invention is derived by reacting, phenol, .dicyandiamideand. formaldehyde inthe proportions of Lmole. of the: phenol, from 0.8 mole to 2 moles of dicyandiamideandfrom 0.5 to 0.9 mole of aqueous formaldehyde per. mole of. the combinedphenol and dicyandiamide.. Water. is present, being usually" furnished. as. part ofthe. aqueous formaldehyde solution (3.7% to.40%-), and. amounting to at least 10% of the weight of the reactants, and ordinarily will not exceed the weight of. the-reactants.v The mixture is reacted in" the presenceofan alkylolamine catalyst for at least /2 hour, and-preferably by. refluxing. for from 1. to 2 hours;.a'nd"is' then vacuum dehydrated under a vacuumof at least; 25. inches of mercury while heatis applied during the evacuation until substantially all the water is removed. The vacuum. dehydration; is. carried out" at a temperature of about C. to C. until a sampleiof theresincooled toroom temperature, 25 C., is brittle. A string of such properly reacted resin at room temperature. breaks when.

bent slightly. When this condition is reachedithere 'isiadd edto the dehydrated reaction ,product agvolhtile-solvent and" a sufiicient amount of heXamethylenetetraminezcom-- pound .to bring the ratio of the total amount ohformalde hyd'e to the combined phenol'anddicyandiarnideto a value.-

of from 0.95" to 1.5. This mixture is then refluxed for atlea'st /2 hour and preferably from. 1. /2: hours to 2 hours.

After this refiuxingperiod. the resin. varnish. is permitted to cool to roomtemperature.

The varnish-may include a small proportion of the order of 2% to 1.0% byweight of. finely divided solids such as silica, aluminum oxide, antimony oxide, andthe like. refractory solids. to impartv better flame resistance;

The resulting impregnatingvarnishis applied tofibrous sheet materials and particularlyv cellulosic fibrous ma terials, such as kraft paper, alpha paper. and cottoncloth. Laminates having exceptional flame resistant properties and high strengths maybe obtained when the varnish is applied to cellulosic materials. However, other fibrous. materials maybe used, such as glass cloth, glass mat, asbestos cloth, nylon'cloth and other synthetic resinous fabrics or mixture of'two or more fibrous materials, such' it is' desirable to heat the fibrous material treated.- withthe varnish composition at a temperature of from 110.. C.

to C. for a brief'period in order tor'emove the solventv therefrom promptly and to advance the cure of theresin. well in to the B stage. The heat treatment of' the apassessar e plied' phenol-dicyandiamidedormaldehyde resin at this stage is conducted so that the resulting treated fabric has a greenness of from 0.5%'to The greenness is determined by placinga small piece of the, resin treated sheet material in a hot press afa' temperature of 175 C. and a pressure of 1 000 pounds per squareinch for 5- min utes, and then measuring the amount of resin that is forced out of the sample, that is, the resin'that extendsbeyond the fibrous sheet material proper, and determining the proportion of this exudedresin to all of the resin in the sample. A greenness of.10% is relatively, high and is desirable for the making of certain'products, ,such as 7 tubes which requirea considerable flow of resin between laminations in order that the laminations bond adequately.

' A greenness of about 0.5% 'on the other hand ,is rela-' tively low but is particularly essential for the purpose of making thick flat laminates. of 1% inch thicknessand greater.- 7 1 The sheet fibrous material, with the applied B stage phenol-dicyandiamide-formaldehyde resinous reaction product thereon,'may be molded into laminates,'tubes and other members by superimposing a plurality of layers of the treated sheet material and compressing them at pressures of from 150 to15000 pounds per square inch attemperatures of from 135 C. to 165 C. It will be appreciated that the fibrous sheet material may be chopped or mace'rated, or otherwise treated, and members molded from such comminuted fibrous material. Of course, the.

' highest strength products are secured with laminates made from superimposed layers of the impregnated fibrous sheet material. The following example is illustrative of the preparation of a phenol dicyandiamide-formaldehyde resin varnish by c r 14.- The mixture was heated slowly, and at SOf CQaneX thermic reaction took place that carried the temperature to approximately 95 C. Additional heatwas thensupplied in order to cause the mixture to reflux. The mixture was refluxed for 2 hours and then dehydratedunder a vacuum of 27 inches of mercury, and'the-temperature gradually increased'to approximately 85 "t C. during dehydration l Substantially all the water was removed.

. Vacuum dehydration was carried out until the resin was a method as set forth in the Baldwin application previously referred to. V

' 7 7 Example 'I Into a steam heated reaction kettle there were intro duced the following: a r

' Parts by weight Phenol 560 Dicyandiamide V 500 Formaldehyde 37 ...r 1160 Ammonia (28%) 22 The ammonia and the formaldehyde were admixed before being introduced into the kettle with the remainder of 'the ingredients, the mixture having a pHof approximately 8.5. The mixture was slowly heated, and at 80 C. an exothermic reaction took place that carried the temperature to approximately 95 C. Additional heat was then supplied in order to cause the reaction mixture to. reflux. The mixture was refluxed for 90 minutes and then. dehydrated under a vacuum of 27 inches of mercury, and the temperature gradually increased to approximately 75 Substantially all the water had. been removed. The resulting reaction product was then C. during dehydration.

Example II Into a'steam-heated reactionvessel there were introduced the following: o

Parts by weight Phenol .120 .Dicy'andiamide V t .105

Formaldehyde (37%) 150,

- platens being at 143 brittle when cooled to room temperature- To there:

action product there were added'the. following." j I I Parts by weight This mixture was then heated slowly to reflux and re fluxed for two hours. At the end'of the reflux period-the, mixture was permitted to cool to room temperature; The resulting 'varnishhad a viscosity of approximately 15 Q centipoises and between 52% and by weightof re; The set time. of the varnish was",

coverableresin solids.

approximately 17 minutes at 153 C. The specific gravity:

of the varnish was'between 1.100 and 1.115. Example III Thevarnish of Example I was employed to impregnate sheets of 12" by 12" by :10 mil thick alpha paper, the; impregnated paper containing 53% of resin'solids at a greenness of,0 .5%. V Laminates were pre'-; pared from the impregnated paper by superimposing; a sufli'cient number of'laminations to produce consolidated members of in thickness. The superimposed layers' were'consolidated' at 1200 pounds per square inch with; the temperature of the press platens being 3tf14 5. C.

Thermocouples were embedded in the laminates and;

the temperature rise noted at various time intervals. maximum temperature rise to 230 C. wasnoted or 85. C. above the temperature of the press platens. Referring to the single figure of the drawing,the temperature rise of the laminate is denoted by the curve 10. It will be noted that the temperature rise is accelerated at a high'rate after it reaches the temperature of the platen as indicated.

by the line 12, thus indicating the large exotherm of this resin.

Example IV a i The varnish of Example 11 was employed tojmpregnate 7 sheets of '12 by 12" 7 by IOmil thick alpha paper, the impregnated paper containing 53% of its weight of the resin solids of a greenuess'of 0.5%.. Three-'quarterinch. laminates were made and tested by the same proceduref employed in Example III, the temperature of the press;

C. A maximum temperature rise to 1 C. was noted or only 27 above the platen tem perature. The temperature rise is indicated by the curvej 14 in the single figure of the drawing. It willbe'noted further-that the. curve 14 shows a slow gradual riseafter the platen temperature is reached as compared to 1 the sudden sharp rise of curve10. c E It will be understood thatthe resinous compositions'of this inventionmay be prepared by substituting cresol for N a part or all of'the phenol. Furthermore, other mono,;

and tri alkylolamine catalysts having alkylol groups having not over 4 carbons'may belemployed in carrying;

outthereactionh Examples of suitable alkylolamine cata lysts are monoethanolanjine, die'th'anolamine and triisopropanolamine. j Mixtures of two or more alkylolamine'si may be" employed. The catalyst may be employed in an amount of from 0.1% up to- 5% based on the weight of the phenol; Ammonia can be substituted for a part of the alkylolamine catalyst ordinarily not exceeding;50%

a by, weight of the catalyst.

In preparing the varnish; impregnating composition" of this invention, I havesecuredparticularly good results by? T riethanolamine w e- 4.8 .75 using as a volatile solvent a mixture. of ethanol and water its weight ,ofjthe' V wherein the water comprised not over 50% by weight of the mixture. However, other alcohols, such as methanol, isopropanol and propanol, may be employed alone or in admixture with the ethanol, or water and ethanol.

It will be understood that the above examples and description are illustrative and not in limitation of the in vention.

I claim as my invention: I

1. In the process of producing a dicyandiamidephenolaldehyde resin varnish, the steps comprising refluxing one mole of a phenol, from 0.8 mole to 2.0 moles of dicyandiamide and from 0.5 to 0.9 mole of aqueous formaldehyde for each mole of the combined phenol and dicyandiamide for a period of time of from /2 hour to 2 hours in the presence of from 0.1% to 5.0%, based on the weight of the phenol, of an alkylolamine catalyst having not over 4 carbon atoms in the alkylol radicals, evacuating the refluxed reaction product to a vacuum of at least 25 inches of mercury while applying heat during the evacuation to a point where a sample of resin is brittle at room temperature, thereafter adding to the refluxed reaction prod not a volatile solvent selected from at least one of the groups consisting of one to three carbon atom monohydric aliphatic alcohols with not over 50 by weight of water, a sufiicient amount of hexamethylenetetramine to bring the ratio of the total amount of formaldehyde to the combined phenol and dicyandiamide to a value of from 0.95 to 1.5, refluxing for a period of time of from V2 hour to 2 hours, and thereafter cooling the varnish to room temperature.

2. The process of claim 1 in which the alkylolamine catalyst is triethanolamine.

3. The process of claim 1 in which ammonia is substituted for a portion of the alkylolamine.

4. A composition of matter comprising a dicyandiamide-phenol-aldehyde resin varnish derived by refluxing one mole of a phenol, from 0.8 mole to 2.0 moles of dicyandiamide and from 0.5 to 0.9 mole of aqueous formaldehyde for each mole of the combined phenol and dicyandiamide for a period of time of from /2 hour to 2 hours in the presence of from 0.1% to 5.0% based on the weight of the phenol, of an alkylolamine catalyst having not over 4 carbon atoms in the alkylol radicals, evacuating the refluxed reaction product to a vacuum of at least 25 inches of mercury while applying heat during the evacuation to a point where a sample of resin is brittle at room temperature, thereafter adding to the refluxed reaction product a volatile solvent selected from at least one of the groups consisting of one to three carbon atom monohydric aliphatic alcohols with not over by weight of water, a suflicient amount of hexamethylenetetrarnine to bring the ratio of the total amount of formaldehyde to the combined phenol and dicyandiamide to a value of from 0.95 to 1.5, refluxing for a period of time of from /2 hour to 2 hours, and thereafter permitting the varnish to cool to room temperature, the varnish comprising from 20% to resin solids.

References Cited in the file of this patent UNITED STATES PATENTS 1,938,917 Loetscher Dec. 12, 1933 2,314,701 Harvey Mar. 23, 1943 2,315,400 DAlelio Mar. 30, 1943 2,606,885 Schmutzler Aug. 12, 1952 2,660,215 Arone Nov. 24, 1953 

1. IN THE PROCESS OF PRODUCING A DICYANDIAMIDEPHENELALDEHYDE RESIN VARNISH, THE STEPS COMPRISING REFLUXING ONE MOLE OF A PHENOL FROM 0.8 MOLE TO 2.0 MOLES OF DICYANDIAMIDE AND FROM 0.5 TO 0.9 MOLE OF AQUEOUS FORMALDEHYDE FOR EACH MOLE OF THE COMBINED PHENOL AND DICYANDIAMIDE FOR A PERIOD OF TIME OF FROM 1/2 HOUR TO 2 HOUR IN THE PRESENCE OF FROM 0.1% TO 5.0%, BASED ON THW WEIGHT OF THE PHENOL, OF AN ALKYLOLAMINE CATALYST HAVING NOT OVER 4 CARBON ATOMS IN THE ALKYLOL RADICALS, EVACUATING THE REFLUXED REACTION PRODUCT TO A VACUUM OF AT LEAST 25 INCHES OF MERCURY WHILE SPPLYING HEAT DURING THE EVACUATION TO A POINT WHERE A SAMPLE OF RESIN IS BRITTLE AT ROOM TEMPERAATURE, THEREAFTER ADDING TO THE REFLUCXED REACTION PRODUCT A VOLATILE SOLVENT SELECTED FROM AT LEAST ONE OF THE GROUPS CONSISTING OF ONE TO THREE CARBON ATOM MONOHYDRIC ALIPHATIC ALCOHOLS WITH NOT OVER 50* BY WEIGHT OF WATER, A SUFFICIENT AMOUNT OF BEXAMETHYLENETERAMINE TO BRING THE RATIO OF THE TOTAL AMOUNT OF FORMALDEHYDE TO THE COMBINED PHENOL AND DISCYANDIAMIDE TO A VALUE OF FROM 0.95 TO 1.5 REFLUXING FOR A PERIOD OF TIME OF FROM 1/2 HOUR TO 2 HOURS, AND THEREAFTER COOLING THE VARNISH TO ROOM TEMPERATURE. 